EP3448809B1 - Anlage zur herstellung eines verbundmaterials mit kohlenstoffnanoröhrchen und verfahren zur durchführung dieser anlage - Google Patents

Anlage zur herstellung eines verbundmaterials mit kohlenstoffnanoröhrchen und verfahren zur durchführung dieser anlage Download PDF

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Publication number
EP3448809B1
EP3448809B1 EP17725310.1A EP17725310A EP3448809B1 EP 3448809 B1 EP3448809 B1 EP 3448809B1 EP 17725310 A EP17725310 A EP 17725310A EP 3448809 B1 EP3448809 B1 EP 3448809B1
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European Patent Office
Prior art keywords
substrate
injection
gas mixture
movement
gas
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English (en)
French (fr)
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EP3448809A1 (de
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Jérémie DESCARPENTRIES
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Nawatechnologies SA
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Nawatechnologies SA
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/164—Preparation involving continuous processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/14—Production of inert gas mixtures; Use of inert gases in general
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1868—Stationary reactors having moving elements inside resulting in a loop-type movement
    • B01J19/1875—Stationary reactors having moving elements inside resulting in a loop-type movement internally, i.e. the mixture circulating inside the vessel such that the upwards stream is separated physically from the downwards stream(s)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
    • B01J8/004—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor by means of a nozzle
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00076—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
    • B01J2219/00085—Plates; Jackets; Cylinders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00162—Controlling or regulating processes controlling the pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00164—Controlling or regulating processes controlling the flow
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/08—Aligned nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/36—Diameter

Definitions

  • the invention relates to the field of reactors for the deposition of carbon nanotubes from a vapor phase on a solid substrate. More particularly, it relates to an installation for the manufacture of a composite material comprising carbon nanotubes, in particular vertically aligned carbon nanotubes (VACNT), deposited on a typically moving substrate. The invention also relates to a method of using this installation.
  • VACNT vertically aligned carbon nanotubes
  • Carbon nanotubes (often abbreviated as “CNT”, Carbon NanoTubes) have walls formed by graphitic mono-sheets (graphene sheets). Whether they are single-sheet wall or multi-sheet wall, they have specific mechanical, thermal, electronic and structural properties; these properties reflect their strong structural anisotropy. Many applications have been imagined taking advantage of these particular properties. Polymer materials loaded with nanotubes were thus prepared, which were used for the manufacture of tennis rackets, taking advantage of mechanical properties combining resistance and flexibility. It has also been envisaged to take advantage of their high electronic conductivity in the direction of the length of the tubes.
  • VACNT Very Aligned Carbon NanoTubes
  • Hu et al. (“3-omega measurements of vertically oriented carbon nanotubes on silicon”, J. Heat Transf. 128 (2006) p.1109-1113 ) describe the possibility of using a VACNT mat as thermal interface materials (TIM).
  • Thermal interface materials are used to remove heat produced by electronic components with which they are in thermal contact. The authors observe on a VACNT carpet deposited on a silicon crystal that the thermal conductivity in the direction of the thickness (ie parallel to the length of the aligned tubes) is much higher than that of the commercially available thermal interface materials.
  • FR 3 013 061 A1 a method of continuously manufacturing nanostructures aligned on a moving support, comprising conveying the support through a heated space and synthesizing, in this space, the nanostructures aligned on the support by catalytic chemical vapor deposition.
  • the heated space is divided into at least two consecutive zones in the direction of conveying the support.
  • the synthesis of nanostructures results from heating operations and injection operations, in each of the aforementioned zones, of a flow of an aerosol containing a catalytic precursor and a source precursor of the material of the nanostructures to be formed, conveyed by a carrier gas.
  • the injection operations are carried out by modifying, in at least two of said zones, a parameter chosen from the flow rate of the flow of the carrier gas and the chemical composition of the carrier gas.
  • the carrier gas can be an inert gas or a reactive gas or an inert gas / reactive gas mixture;
  • the aerosol, for its part corresponds to the dispersion, in the form of droplets, of the liquid or of the solution containing the catalytic precursor and / or the source precursor in the carrier gas, this dispersion being obtained by spraying or by nebulization of the liquid or the solution in the carrier gas.
  • EP 2 397 441 and US 2013/189432 describe various embodiments of devices intended for the production of carbon nanotubes. These devices include in particular gas injection sections, involving injection members of the shower head type, or of the perforated plate type.
  • an objective of the present invention is therefore to remedy, at least partially, the drawbacks of the prior art mentioned above.
  • Another objective of the invention is to provide an installation making it possible to implement, in a manner that is both simple and efficient, a method of manufacturing a composite material comprising carbon nanotubes.
  • Another objective of the invention is to provide such an installation which is accompanied by flexible implementation, so as to conveniently vary the parameters of the process.
  • Another objective of the invention is to provide such an installation, which has a modular structure, while remaining satisfactorily simple.
  • FIG. 1 The appended figures describe an embodiment of an installation according to the invention.
  • three axes have been carried, namely a longitudinal axis XX of the installation, a so-called lateral or transverse YY axis, as well as a vertical ZZ axis.
  • the enclosure 1 has two main zones, respectively lower 2 and upper 3 (see in particular figure 2 ), which are separated by a horizontal sole 10 which will be described in more detail in what follows.
  • these zones 2 and 3 are physically separated by a fixed mechanical member, namely the aforementioned sole. It will be noted however that, in other embodiments of the invention, not shown, such a fixed member is not provided, so that these two zones are delimited by the substrate proper.
  • the lower zone 2 extends over a height H2 which is typically between 10% and 50% of the total height H1 defined above. It is bordered by different walls, namely opposite front walls 21 and rear 22, opposite side walls, as well as a bottom wall 25.
  • the sole 10 is typically formed by a metal sheet, the thickness of which is for example between 3 mm and 20 mm, the material of which is adapted to the process temperature. It can be placed on a frame to promote thermal expansion. It is also possible to use a graphite plate. The sole is stationary with respect to the walls of the enclosure.
  • the aforementioned walls of the lower zone 2 define, with the sole 10, a reception volume for heating modules 26, of a type known per se.
  • These modules 26 are arranged one behind the other, along the axis XX.
  • each module can be replaced independently of the others, which ensures convenient maintenance.
  • each module 26 comprises an upper heating element 26 ', arranged immediately below the sole 10, as well as a lower stack of insulating plates 26 ".
  • these heating elements 26' are ceramic elements.
  • they can allow heating by radiation, for example they can be infrared emitters.
  • the upper zone 3 is bordered by different walls, namely opposite front walls 31 and rear 32, opposite side walls, as well as a roof wall 35. On their inner face, these walls are covered by means of stacks of plates 36, having a thermal insulation function.
  • the facing front walls 21 and 31 define an entrance E1 of the enclosure, while the facing rear walls 22 and 32 define an outlet S1 of this enclosure.
  • This inlet and this outlet which have a height for example between 0.2 cm and 1.0 cm, extend over a width for example between 10 and 150 cm.
  • the upper zone of the enclosure 1 successively defines an upstream preheating region 37, as well as a reaction chamber 4, also called the treatment chamber, which will be described in more detail in what follows.
  • a reaction chamber 4 also called the treatment chamber
  • the length L37 of this preheating region 37 is between 20 and 100 cm, while the length L4 of this reaction chamber 4 is between 70 and 230 cm. It will therefore be noted that the figures 1 and 2 are not to scale, in order to illustrate more clearly the reaction chamber 4.
  • the preheating region 37 is equipped in particular with a tension roller 38, of a type known per se.
  • the installation according to the invention for the manufacture of a composite material comprising carbon nanotubes, is designed to operate at a pressure in the reaction chamber 4 which is typically close to atmospheric pressure. More precisely, it is advantageously between 0.6 bar and 1.4 bar, more advantageously between 0.7 bar and 1.3 bar, more preferably between 0.8 bar and 1.2 bar, even more preferably between 0, 9 bar and 1.1 bar, and optimally between 0.95 bar and 1 bar.
  • a range of between 0.9 bar and 1.1 bar, in particular between 0.95 bar and 1 bar, makes it possible, among other things, not to exert excessive mechanical stresses on the various components of the installation.
  • the latter may, therefore, have a reasonable weight.
  • the reaction chamber 4 is placed under a slight pressure, relative to the rest of the enclosure 1. This makes it possible to guarantee satisfactory confinement of the reactive gases, inside this chamber 4.
  • the difference between the pressure P1 of the rest of the chamber 1 and the pressure P4 of the chamber 4 is between 1 and 20 Pa, in particular between 2 and 10 Pa, typically close to 5 Pa.
  • the value of P1 can be slightly lower than atmospheric pressure, for example between 10 and 100 Pa, in particular between 30 and 70 Pa, typically 50 Pa below this atmospheric pressure value.
  • the figures 15 and 16 illustrate the module 5 according to two different cutting lines, taken at a distance from each other along the lateral axis YY.
  • the figure 15 is a view in median section, namely along the line XV-XV which corresponds to the median longitudinal axis XX, while figure 16 is a sectional view along the line XVI-XVI, which extends between the middle of the enclosure and one of the lateral edges of this enclosure.
  • module 5 includes a base plate 50 (also visible on the figure 3 ), the thickness of which is for example between 0.5 cm and 2.0 cm.
  • the length L5 of this module namely its dimension along the axis XX, is for example between 20 cm and 60 cm.
  • the width I 5 of this module namely its dimension along the YY axis, is for example between 20 cm and 55 cm.
  • this plate 50 is provided with means allowing its removable fixing, either on an identical plate belonging to the neighboring module, or on one or the other of the devices 7 or 7 '.
  • this plate 50 can for example find respectively tenons and mortises not shown, allowing fixing by interlocking with a complementary element, also not shown.
  • This plate 50 is first of all pierced with orifices 52 intended for the injection of gas in the direction of the substrate, which extend between the opposite faces of this plate.
  • these orifices are substantially vertical.
  • the outlet of these orifices is advantageously turned downstream, with reference to the direction of travel of the substrate.
  • a fillet not shown is arranged at the end of each hole, intended to facilitate the distribution of the gas.
  • This plate 50 is also pierced, in its thickness, with transverse orifices 53 which connect the lateral faces of this plate.
  • Each orifice is placed in communication with an inlet or an outlet of a heat transfer fluid, typically water.
  • a heat transfer fluid typically water.
  • This communication is for example carried out by means of end pieces, shown schematically.
  • the module 5 comprises, in addition to the aforementioned plate 50 , a hollow body 60 forming a cover, which is fixed to the upper face of the plate by any suitable means.
  • a removable fixing means will be preferred, for example tenon and mortise type.
  • This cover 60 is equipped, at its upper part, with a neck 61 ( figures 4 and 15 ) delimiting an inlet channel 61 ′ of the gases.
  • This neck is placed in communication, by any suitable means, with a not shown source of supply of reactive gases.
  • This channel 61 ' opens laterally into horizontal passages 62, provided in the upper part of the cover, which communicate with diffusion members 63. As shown in particular by figure 4 , these passages 62 extend in a star from the neck 61.
  • the number of diffusion members 63, for each module 5, is for example between one and ten. In the example illustrated, there are four diffusion organs, the arrangement of which is visible on the figure 4 .
  • Each diffusion member 63 first of all comprises a vertical tube 64 , in which are formed, perpendicular to the surface of this tube, orifices 64 ′ , the dimensions of which are typically from 0.2mm to 1mm.
  • Each member 63 further comprises a diffusion element 65, said to be in the form of an inverted parasol, the concavity of which is turned towards the top of the cover. It will be noted that the various diffusion elements 65 are not placed along the median longitudinal axis XX. In this way, they are cut in the middle on the figure 16 , but on the other hand not on the figure 15 .
  • each module 5, 5 ', 5 " is movable along the ZZ axis relative to the sole 10, so as to vary the height of the reaction chamber 4.
  • the first circulation device 7 comprises a body 70 delimiting an internal volume V70 bordered by peripheral walls 71, an upper wall 72 and a plate forming the bottom wall 73.
  • the latter which extends obliquely, is provided with removable fixing means, both on the adjacent module 5 and on the upstream unit 8.
  • tenons not shown fitted to the wall 73 can penetrate into mortises which are also not shown, formed in the walls facing respectively the module 5 and the unit 8.
  • the oblique plate 73 is hollowed out with circulation orifices, regularly distributed.
  • Each orifice 75 has an upper section 751 oblique, extending approximately perpendicular to the plane of the plate 73, as well as a lower section 752 extending horizontally, namely substantially parallel to the direction of travel of the substrate.
  • the plate 73 is also pierced with side tubes 75 ', intended for the flow of a heat transfer fluid, in particular water, to cool the part 73.
  • the body 70 is equipped, at its upper part, with at least one neck delimiting a gas circulation channel, which opens into the aforementioned interior volume.
  • at least one neck delimiting a gas circulation channel which opens into the aforementioned interior volume.
  • two identical necks can be provided, provided one behind the other along the lateral axis YY. So on the figure 6 , one 76 of these necks is illustrated, it being understood that the other is located behind the one which is visible.
  • each neck can be selectively connected, either to a source of reactive gases, or to a source of depressurization.
  • the device 7 is also equipped with two deflectors 77 and 78, produced for example in the form of thin sheets. These deflectors, which are fixed to the walls of the body 70 by any suitable means, define a generally Z-shaped gas path between the intake channel and the injection orifices. This makes it possible to lengthen this path and, consequently, to increase the residence time of the reactive gases and to homogenize the gases in the volume V70.
  • the path of the reactive gases is shown by the various arrows R '.
  • the structure of the device 7 ' is preferably identical to that of the device 7, as described above. This is advantageous, in particular in terms of the overall simplicity of construction of the installation according to the invention.
  • the mechanical elements of this device 7 ′ which correspond to those of the device 7, are assigned the same reference numbers to which the suffix “prime” is added.
  • these two devices 7 and 7 ' are arranged mutually symmetrically, with respect to a median transverse plane of the reaction chamber.
  • the first barrier gas distribution unit 8 comprises a body 80 delimiting an internal volume V80 bordered by peripheral walls 81, an upper wall 82 and a bottom plate 83.
  • the latter is provided with mortises, not shown, capable of cooperating with the tenons equipping the adjacent device 7, with a view to the mutual removable fixing of this unit 8 and of this device 7.
  • the plate 83 is hollowed out with distribution slots 85, which are shown seen from below at the bottom. figure 8 .
  • These slots 85 are distributed along three lines L85, advantageously arranged in staggered rows.
  • each slit 85 has a length of between 0.3 cm and 1.0 cm, as well as a width of between 0.02 cm and 0.5 cm.
  • the slots are formed inclined relative to the vertical, at an angle A85 of for example between 0 ° and 60 °. In other words, these slots allow a distribution of gas directed towards the inlet of the reaction chamber 4, namely in a direction opposite to that of the travel of the substrate.
  • the body 80 is finally equipped, at its upper part, with at least one neck defining a gas inlet channel, which opens into the aforementioned interior volume.
  • at least one neck defining a gas inlet channel, which opens into the aforementioned interior volume.
  • two identical necks can be provided, provided one behind the other along the lateral axis YY. So on the figure 7 , one 86 of these necks is illustrated, it being understood that the other is located behind the one which is visible. As will be seen in what follows, this neck can be connected to a source of neutral gas. On the figure 7 , the path of the neutral gas is shown by the various arrows N.
  • unit 8 ' is preferably identical to that of unit 8, as described above.
  • the mechanical elements of this unit 8 ′ which correspond to those of the unit 8, are assigned the same reference numbers to which the suffix “prime” is added.
  • these two units 8 and 8 ' are arranged mutually symmetrically, with respect to a median transverse plane of the reaction chamber.
  • the barrier gas distribution slits are directed towards the outside of the reaction chamber 4, namely that the slits of the upstream unit 8 face upstream, while the slits of the downstream unit 8 ' are facing downstream.
  • the main enclosure 1 is made in the form of a box, having respectively front walls 11 and rear (not shown), in which respective slots are formed, of which only that 13 is illustrated. These slits, which extend only over part of the width of box 1, respectively define the input E1 and the output S1 of the enclosure.
  • This box 1 further comprises a bottom 15, side walls 16, as well as an upper wall 17.
  • the latter is made in the form of a pivoting hatch, rotatably mounted on the top of one of the side walls around it. an axis A17, parallel to the longitudinal direction of the enclosure, namely the direction of travel of the substrate.
  • the various mechanical members 5, 5 ', 5 ", 7, 7', 8 and 8 ', described above, are fixed to the hatch 17.
  • this fixing is of the type. removable
  • the embodiment, illustrated in this figure 11 has specific advantages. In fact, an operator is able to easily lift the hatch so as to access the interior volume of the enclosure 1. Under these conditions, he can conveniently carry out cleaning, in particular any carbonaceous deposits liable to be. present on the aforementioned mechanical components and / or on the interior walls.
  • the suction assembly 9 comprises a common transition box 90, into which respectively open an inlet corridor 91, two extraction pipes 92, as well as a junction corridor 93.
  • the inlet corridor 91, or downstream lane allows the supply of the substrate to the box 90.
  • the junction lane 93, or downstream lane allows the transfer between this box and the input E1 of the main enclosure.
  • These two corridors have shapes and dimensions adapted to those of the moving substrate. In the example illustrated, they are therefore rectangular in shape.
  • an intermediate space that is as small as possible is provided between the facing faces of this substrate and of each of these corridors.
  • the box 90 has the overall shape of a diamond. In other words, its section continuously decreases, from its junction with each of the corridors 91 and 93, towards its junction with each of the pipes 92.
  • Each pipe 92 has a tubular shape, for example substantially cylindrical, the section of which is for example included. between 15 and 60 millimeters. It is placed in communication with a source of depressurization, not shown, of any suitable type.
  • the structure of the assembly 9 ' is preferably identical to that of the assembly 9, as described above.
  • the mechanical elements of this assembly 9 ′ which correspond to those of the assembly 9, are assigned the same reference numbers to which the suffix “prime” is added.
  • these two sets suction 9 and 9 ' are arranged mutually symmetrically, with respect to a transverse plane of the installation.
  • an additional plate 95 forming a complementary injection member.
  • This plate 95 of the blade or air knife type, is provided between the junction corridor 93 and the front walls 21 and 31 of the enclosure 1, delimiting the entrance E1.
  • This plate 95 of rectangular shape, is hollowed out with a main slot 96 extending in the extension of both the junction corridor 93 and the aforementioned entrance E1.
  • various orifices extend in the plate, so as to connect the slot 96 with the upper and lower walls respectively of the plate 95.
  • 97 are noted the upper orifices, of which the outlets 97 ' opposite to the slot are visible, as well as 98 the lower orifices, of which the outlets 98 ' adjacent to the slot are visible.
  • the path of these orifices 97 and 98 is shown in dotted lines, on this figure 18 .
  • Each orifice 97, 97 ' is placed in communication with a source, not shown, of barrier gas, in particular nitrogen.
  • this plate 95 with respect to both the passage 93 and the reaction chamber 4, is ensured by any suitable means.
  • a removable type of attachment for example by screwing, will be preferred.
  • sealing means are provided, not shown in the figures 17 and 18 . These means, of any type known per se, provide sealing between the facing faces, on the one hand of the plate 95 and the passage 93, on the other hand of the plate 95 and of the chamber 4.
  • the plate has a thickness E95 typically close to 10 millimeters
  • the slot has a width I96 typically close to 5 millimeters
  • each orifice has a diameter d97 typically close to 4.5 millimeters.
  • a source 100 of reactive gases a source 200 for depressurizing, a source 300 of a barrier gas, as well as connections C5, C7, C7 ′, C8 and C8 ′.
  • connections can be of any suitable type: connections of single type and / or connections of multiple type can thus be provided.
  • the scrolling of the substrate is operated according to a “roll to roll” process, of a type known per se.
  • the substrate is supplied from an upstream coil to a downstream coil, both not shown.
  • the substrate may in particular be a metal sheet or strip, or else a carbon fabric. Its thickness can typically be between 15 ⁇ m and 200 ⁇ m, and its width between 10 mm and 1000 mm or more.
  • the constituent metal of the substrate is, for example, pure aluminum or another grade of aluminum, or else stainless steel.
  • the reaction is carried out on a moving substrate.
  • the substrate is admitted to the inlet of the installation, then scrolls continuously while being subjected to the desired reaction.
  • the arrows S show the displacement of this substrate.
  • the substrate when the substrate progresses in the inlet passage 91, it carries with it on its two faces an ambient air flow, materialized on the figure 9 by the AIR arrow.
  • This flow of ambient air is opposed to a flow of barrier gas which prevents any significant entry of this ambient air, in the direction of the main enclosure 1.
  • This barrier gas is formed by the mixture between the neutral gas N, injected by unit 8, and an inerting gas.
  • a first fraction of inerting gas is injected into the lower part 2, according to the arrows I1. This gas makes it possible to expel the air from this lower part towards the upper part. The passage of this inerting gas and this air is permitted by the presence of interstices existing at the interface between these two parts.
  • a second fraction of inerting gas is injected into the main chamber, according to the arrows I2. This injection is preferably carried out both upstream and downstream of this main chamber.
  • the inerting gas injected at the same time according to I1 and I2, is mixed with the neutral gas N injected through the slots 85 of each unit 8 (see figure 7 ). This mixture forms a barrier gas, the flow of which is indicated by the arrow B on the figure 9 .
  • the vacuum sources are also activated, so that this barrier gas B blocks the ambient air, at the level of the transition box.
  • This air and this barrier gas are evacuated through the pipes 92 according to the arrows F92, shown on the figures 9 and 10 .
  • the flow of barrier gas also makes it possible to prevent the exit of the reaction gas chamber through the passage 91; in fact, the flow of barrier gas is advantageously evacuated through the pipes 92 to a gas processing center (not shown in the figures).
  • This injection can be carried out permanently, or even on an ad hoc basis. It makes it possible to produce a barrier gas curtain or knife, which is useful in particular in the event of failure of the transition boxes 90 and / or of untimely entry of oxygen into the reaction chamber.
  • the use of this complementary injection plate 95 also makes it possible to reduce the quantity of oxygen in the main chamber.
  • the substrate After having encountered the flow of barrier gas in the passage 93, the substrate progresses into the preheating zone, where it is first of all pressed against the sole 10, by means of the tension roller 38. Then this substrate is brought to an appropriate temperature for the desired treatment.
  • this temperature is lower than the melting point of the metal, ie about 650 ° C. Since the substrate is kept under tension and exhibits an elongation which increases with temperature, it is very particularly preferred to place it at a temperature well below this melting temperature, that is to say preferably at a temperature which does not. not exceed 620 ° C to 630 ° C.
  • the heating is carried out by mechanical contact rubbing the substrate on the sole 10, itself heated from its lower surface by the heating elements.
  • This fixed sole which delimits the reaction chamber 4 as explained above, is advantageous in that it prevents the deposition of nanotubes on the heating elements.
  • a deposit on the two opposite faces of the substrate not shown in the figures, it is possible to envisage a deposit on the two opposite faces of the substrate. In this case, a radiant heating is preferred.
  • the nanotubes are black, they absorb infrared radiation.
  • Reactive gases include a "carbon source” gas and a catalyst.
  • the catalyst can advantageously be ferrocene.
  • the “carbon source” gas can be C 2 H 2 .
  • the injection of reactive gases is carried out as follows. The preferred catalyst being a fairly poorly soluble solid, a sufficient catalyst concentration will not be obtained in solution to be able to evaporate it in the carrier gas “carbon source” before the introduction. It is therefore injected as an aerosol, and it is assumed that before coming into contact with the substrate these droplets evaporate completely. The gas phase in contact with the substrate is therefore homogeneous.
  • downstream assembly 9 ' and the downstream unit 8' cooperate with each other, in an identical manner to what has been described above for the upstream assembly 9 and the upstream unit 8.
  • the injection of barrier gas is indicated by the arrow F8 ' on the figures 12 to 14 .
  • the upstream device 7 is used in “injection” mode. Under these conditions, its neck 76 is connected to the source 100 of reactive gas mixture. The latter therefore flows, in service, from this source to the volume V70, before being injected into the chamber via the orifices 75. This mixture is therefore transported, in this chamber 4, in a direction parallel to that of travel. of the substrate, and in the same direction. This gas mixture transport is shown by the arrow F7 on the figure 12 .
  • the downstream device 7 ′ is used in “suction” or “extraction” mode. Under these conditions, Under these conditions, its neck 76 ′ is connected to the source 200 for depressurizing. The gas mixture is therefore sucked, in service, from the chamber 4 to the volume V70 ′, via the orifices. This gas mixture extraction is shown by the arrow F7 ' on the figure 12 .
  • the devices 7 and 7 ' are both used in “suction” or “extraction” mode. Under these conditions, they are both connected to the source 200.
  • This double extraction of the gas mixture is shown by the respective arrows G7 and F7 ' on the figure 13 .
  • Part of the mixture is therefore transported in a direction parallel to that of travel of the substrate and in the same direction, while another part of this mixture is transported in a direction parallel to that of travel of the substrate but in the opposite direction.
  • Reactive gas injection is therefore carried out only from the 5 to 5 "modules.
  • the upstream device 7 is used in “extraction” mode, so that it is connected to the source 200.
  • the downstream device 7 ′ is used in “injection” mode, so that it is connected to the source 100.
  • the gas mixture is therefore transported, in chamber 4, in a direction parallel to that of travel of the substrate, but in an opposite direction.
  • the gas flow rate and / or the reactant concentration can be different from each other for the modules 5, 5 ', 5 " and, if necessary appropriate, for the device 7 or 7 '.
  • the gas flow rate and / or the reactant concentration may be different.
  • the concentration of reagent decreases along the reaction chamber, which tends to modify the growth of these VACNTs.
  • the fact of adjusting the flow rate and / or the concentration in the two modules 5 ′ and 5 ′′ makes it possible in particular to maintain a substantially constant concentration along the chamber.
  • the figure 19 illustrates an advantageous variant of the invention, relating to the transition box 90 illustrated in figures 9 and 10 .
  • two plates 94 forming deflectors extend in the direction DS of travel of the substrate, on either side of the latter. These deflectors 94 are placed facing the outlets of the two extraction pipes 92, while protruding longitudinally both in the arrival corridor 91 and the junction corridor 93. In transverse view, these deflectors advantageously extend over a substantial part of the aforementioned box 90.
  • the figure 20 illustrates an advantageous variant of the invention, similar to that shown in figure 19 , concerning the additional injection plate 95 illustrated in figures 17 and 18 .
  • two plates 99 forming deflectors similar to those 94 of the figure 19 , extend in the direction of travel of the substrate, on either side of the latter. These deflectors 99 are placed, inside the slot 96, facing the outlets of the orifices 97 and 98. In transverse view, these deflectors advantageously extend over a substantial part of the aforementioned box 90.
  • the respective deflectors 94 and 99, described above with reference to figures 19 and 20 have specific advantages. Indeed, the Applicant has observed that the use of these deflectors makes it possible to reduce the mechanical disturbance undergone by the moving substrate.
  • the aforementioned flows are respectively evacuated or admitted perpendicular to this direction of travel. In the latter case, there is a tendency to observe an instability of the substrate, the appearance of vibrations undergone by the latter, as well as an unstable balance of forces exerted on this substrate.
  • deflectors 94 and 99 are also advantageous in that they guarantee increased safety for the installation.
  • the dynamics of the fluids are very little, if at all, modified by the presence or absence of the substrate.
  • the air does not substantially penetrate, even in the absence of the substrate, which would be due in particular to an accidental rupture of the latter.
  • Such an accidental situation would therefore be, despite everything, stable and not very disturbing for the substrate.
  • the overall efficiency is therefore independent of the presence of the substrate.
  • CNTs carbon nanotubes
  • the catalytic source in particular ferrocene
  • ferrocene is dissolved in a toluene solution at different percentages. Ferrocene decomposes at a temperature of 826 ° C, allowing growth of CNT at 850 ° C.
  • ferrocene does not decompose, so it is necessary to use hydrogen to lower the decomposition temperature of ferrocene to between 400 ° C and 450 ° C.
  • Synthesis No. 1 is carried out statically for a synthesis duration of 60min.
  • a carpet of carbon nanotubes of about 120 micrometers ( ⁇ m) is obtained.
  • Synthesis N ° 2 which is carried out in Roll to Roll, makes it possible to obtain a height of 20 ⁇ m. In this case, the residence time of the substrate in the reaction chamber was shorter due to the displacement of the substrate.
  • the figures 21 and 22 appended show, respectively at low and at high magnification, an example of growth of VACNT (vertically aligned carbon nanotubes) on the aluminum alloy AlMn1 above, for synthesis condition 1 as described above.
  • VACNT vertical aligned carbon nanotubes
  • the figures 23 to 26 appended illustrate different aspects of Synthesis 2, as described above.
  • the figure 23 first of all shows carbon nanotubes on an aluminum substrate, in roll to roll mode, at the exit of the installation where this synthesis took place.
  • the figure 24 shows this same aluminum substrate and the VACNTs wound onto an exit roll.
  • the figures 25 and 26 appended similar to those 21 and 22 mentioned above, show respectively at low and high magnification images of this synthesis 2 on this aluminum alloy AlMn1 with these VACNTs.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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Claims (15)

  1. Anlage zur Herstellung eines Verbundmaterials Kohlenstoffnanoröhrchen umfassend, wobei diese Anlage Folgendes beinhaltet
    - mindestens eine Behandlungskammer, oder Reaktionskammer (4), welche Injektionsmittel (5, 5', 5") eines aktiven Gasgemisches in das Innenvolumen dieser Kammer umfasst, wobei dieses Gasgemisch für das Wachstum der Kohlenstoffnanoröhrchen bestimmt ist,
    - Transportmittel eines Substrats, welches dazu bestimmt ist, das Verbundmaterial zu bilden, in Form eines Blattes oder Streifens, in die Kammer,
    dadurch gekennzeichnet, dass
    die Injektionsmittel imstande sind, das aktive Gemisch in einer ersten Richtung in das Innenvolumen zu transportieren,
    und dadurch, dass die Anlage weiter Mittel zum in Umlauf bringen (7, 7') des Gasgemisches beinhaltet, die imstande sind, das aktive Gemisch in einer zweiten Richtung in das Innenvolumen zu transportieren, die sich von der ersten Richtung unterscheidet,
    wobei die Mittel zum in Umlauf bringen eine erste Injektionskonfiguration des aktiven Gasgemisches in das Innenvolumen dieser Kammer, sowie eine zweite Austragskonfiguration des aktiven Gasgemisches aus dem Innenvolumen annehmen können, wobei festzuhalten ist, dass vorzugsweise:
    die erste Richtung im Wesentlichen senkrecht zu der Vorlaufrichtung des Substrats in die Kammer ist, während die zweite Richtung im Wesentlichen parallel zu der Vorlaufrichtung des Substrats liegt.
  2. Anlage nach dem vorstehenden Anspruch, dadurch gekennzeichnet, dass die Mittel zum in Umlauf bringen mindestens zwei Vorrichtungen zum in Umlauf bringen, jeweils stromaufwärts (7) und stromabwärts (7') umfassen, die auf jeder Seite der Injektionsmittel (5, 5', 5"), in Bezug auf die Vorlaufrichtung des Substrats vorgesehen sind, wobei festzuhalten ist, dass vorzugsweise jede Vorrichtung zum in Umlauf bringen (7, 7') mit Verbindungsmitteln (C7, C7') ausgestattet ist, die geeignet sind, um selektiv entweder an eine Gasgemisch-Quelle (100), oder an eine Unterdruck-Quelle (200) angeschlossen zu werden.
  3. Anlage nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die Injektionsmittel mindestens ein Injektionsmodul (5, 5', 5") umfassen, wobei jedes Injektionsmodul eine Lochplatte (50) zum Verteilen eines Gasgemisches, sowie eine Abdeckung (60) umfasst, die ein Volumen (64) zur Homogenisierung des Gemisches begrenzt.
  4. Anlage nach dem vorstehenden Anspruch, dadurch gekennzeichnet, dass jedes Injektionsmodul (5, 5', 5") ein Verteilungsorgan (65) in der Form eines umgekehrten Regenschirms umfasst, welches zum Verteilen des Gases im Innenvolumen des Moduls geeignet ist.
  5. Anlage nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass sie weiter mindestens zwei Einheiten (8, 8') zum Bereitstellen eines Sperrgases umfasst, welche auf jeder Seite der Injektionsmittel, in Bezug auf die Vorlaufrichtung des Substrats vorgesehen sind.
  6. Anlage nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die Injektionsmittel (5, 5', 5"), die Mittel zum in Umlauf bringen (7, 7') und eventuell die Einheiten zum Bereitstellen eines Sperrgases (8, 8') in einem Einschluss (1) aufgenommen sind, wobei der Einschluss weiter Mittel zum Erwärmen (26) umfasst.
  7. Anlage nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass sie weiter mindestens zwei Gasabsauganordnungen (9, 9') umfasst, die auf jeder Seite der Injektionsmittel in Bezug auf die Vorlaufrichtung des Substrats vorgesehen sind.
  8. Anlage nach dem vorstehenden Anspruch, dadurch gekennzeichnet, dass die Gasabsauganordnung (9) zwei Austragsleitungen (92) umfasst, in denen das Gas in Bezug auf die Vorlaufrichtung (DS) des Substrats querlaufend strömt, und diese Absauganordnung mit zwei Abweisern (94) ausgestattet ist, die sich im Wesentlichen parallel zu der Vorlaufrichtung des Substrats erstrecken, wobei jeder Abweiser gegenüber mindestens einem Teil der Mündung einer jeweiligen Austragsleitung platziert ist.
  9. Anlage nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass sie weiter ein ergänzendes Gasinjektionsorgan (95) umfasst, das zwischen der stromaufwärtigen Gasabsauganordnung (9) und dem Eingang (E1) der Reaktionskammer eingesetzt ist,
    wobei festzuhalten ist, dass das ergänzende Gasinjektionsorgan (95) vorzugsweise zwei Reihen von Injektionsöffnungen (97, 98) umfasst, in denen das Gas in Bezug auf die Vorlaufrichtung (DS) des Substrats querlaufend strömt, und dieses ergänzende Injektionsorgan mit zwei Abweisern (99) ausgestattet ist, die sich im Wesentlichen parallel zu der Vorlaufrichtung des Substrats erstrecken, wobei jeder Abweiser gegenüber mindestens einem Teil der Mündung einer jeweiligen Reihe von Injektionsöffnungen platziert ist.
  10. Verfahren zur Durchführung der Anlage nach einem der vorstehenden Ansprüche, wobei:
    - die Injektionsmittel (5, 5', 5") aktiviert werden, um aktives Gasgemisch in das Innenvolumen der Kammer (4) in der ersten Richtung einzulassen;
    - Mittel zum in Umlauf bringen (7, 7') aktiviert werden, um dieses aktive Gasgemisch entlang dieser Kammer in einer zweiten Richtung zu transportieren;
    - das Substrat in der Kammer vorlaufen gelassen wird, um Kohlenstoffnanoröhrchen an der Oberfläche dieses Substrats zu bilden.
  11. Verfahren nach Anspruch 10, wobei das aktive Gasgemisch in einer Richtung parallel zur Vorlaufrichtung des Substrats transportiert wird, eine erste Fraktion eines aktiven Gasgemisches durch die Injektionsmittel eingelassen wird und eine zweite Fraktion des aktiven Gasgemisches durch die Mittel zum in Umlauf bringen eingelassen wird.
  12. Verfahren nach Anspruch 11, wobei die zweite Fraktion des aktiven Gasgemisches stromaufwärts der Reaktionskammer eingelassen wird, sodass das aktive Gasgemisch in derselben Richtung wie der Vorlaufrichtung des Substrats transportiert wird.
  13. Verfahren nach Anspruch 11, wobei die zweite Fraktion des aktiven Gasgemisches stromabwärts der Reaktionskammer eingelassen wird, sodass das aktive Gasgemisch in der entgegengesetzten Richtung zur Vorlaufrichtung des Substrats transportiert wird.
  14. Verfahren nach Anspruch 10, wobei das gesamte aktive Gasgemisch durch die Injektionsmittel eingelassen wird, und die beiden, jeweils stromaufwärtigen und stromabwärtigen Mittel zum in Umlauf bringen aktiviert werden, sodass ein Teil des aktiven Gasgemisches in derselben Richtung wie der Vorlaufrichtung des Substrats transportiert wird, während ein anderer Teil des Gasgemisches in der entgegengesetzten Richtung zur Vorlaufrichtung des Substrats transportiert wird.
  15. Verfahren nach einem der Ansprüche 10 bis 14, zur Durchführung der Anlage nach einem der Ansprüche 6 oder 7, Verfahren, bei dem die Reaktionskammer (4) in Bezug auf den Rest des Einschlusses (1) in Unterdruck platziert wird, wobei die Differenz zwischen dem Druck (P1) des Rests des Einschlusses (1) und dem Druck (P4) der Reaktionskammer zwischen 1 und 20 Pa, insbesondere zwischen 2 und 10 Pa enthalten ist, insbesondere nahe 5 Pa gelegen ist.
EP17725310.1A 2016-04-25 2017-04-25 Anlage zur herstellung eines verbundmaterials mit kohlenstoffnanoröhrchen und verfahren zur durchführung dieser anlage Active EP3448809B1 (de)

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FR1653606A FR3050449B1 (fr) 2016-04-25 2016-04-25 Installation pour la fabrication d'un materiau composite comprenant des nanotubes de carbone, et procede de mise en oeuvre de cette installation
PCT/FR2017/050976 WO2017187080A1 (fr) 2016-04-25 2017-04-25 Installation pour la fabrication d'un matériau composite comprenant des nanotubes de carbone, et procédé de mise en oeuvre de cette installation

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US7160531B1 (en) * 2001-05-08 2007-01-09 University Of Kentucky Research Foundation Process for the continuous production of aligned carbon nanotubes
CN102307808B (zh) * 2009-02-10 2013-07-10 日本瑞翁株式会社 取向碳纳米管集合体的制造装置
JP5534133B2 (ja) * 2009-03-14 2014-06-25 大陽日酸株式会社 配向カーボンナノチューブ連続合成方法及び同連続合成装置
KR101621581B1 (ko) * 2009-07-01 2016-05-16 니폰 제온 가부시키가이샤 카본 나노 튜브 배향 집합체의 제조 장치
CN103889890A (zh) * 2011-10-19 2014-06-25 应用纳米结构解决方案有限责任公司 用于在可重复使用的基材上连续生产碳纳米结构的系统和方法
JP5850236B2 (ja) * 2012-01-20 2016-02-03 アイシン精機株式会社 カーボンナノチューブの製造装置及びカーボンナノチューブの製造方法
FR3013061B1 (fr) 2013-11-14 2018-03-02 Commissariat A L'energie Atomique Et Aux Energies Alternatives Procede de fabrication au defile et en continu de nanostructures alignees sur un support et dispositif associe

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FR3050449A1 (fr) 2017-10-27
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WO2017187080A1 (fr) 2017-11-02
US11358867B2 (en) 2022-06-14
US20210371285A1 (en) 2021-12-02
EP3448809A1 (de) 2019-03-06

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